AU2007211515A1 - Use of secondary sterically hindered amines as processing additives in rotomolding processes - Google Patents

Description

WO 2007/088130 PCT/EP2007/050678 Use of Secondary Sterically Hindered Amines as Processinq Additives in Rotomoldinq Processes The instant invention pertains to the use of secondary sterically hindered amines as processing additives in rotational molding processes. These additives increase process 5 stability, since they provide a broader temperature range towards higher temperatures during the melt processing step. Rotational molding is a highly versatile manufacturing option that allows for unlimited design possibilities with the added benefit of low production costs. 10 The rotational molding process (rotomolding process) starts with a good quality mold that is placed in a molding machine that has a loading, heating, and cooling area. Several molds may be placed on the machine at the same time. Pre-measured plastic resin 15 is loaded into each mold, and then the molds are moved into the oven where they are slowly rotated on both the vertical and horizontal axis. The melting resin sticks to the hot mold and coats every surface evenly. The mold continues to rotate during the cooling cycle so the parts retain an even wall thickness. 20 Once the parts are cooled, they are released from the mold. The rotational speed, heating and cooling times may be all controlled throughout the process. Rotational molding offers design advantages over other molding processes. With proper design, parts that are assembled from several pieces can be molded as one part, eliminating 25 expensive fabrication costs. The process also has a number of inherent design strengths, such as consistent wall thickness and strong outside corners that are virtually stress free. If additional strength is required, reinforcing ribs can be designed into the part. 30 Rotational molding delivers the product the designer envisions. Designers can select the best material for their application, including materials that meet FDA requirements. Additives to help make the part weather resistant, flame retardant, or static free can be specified.

WO 2007/088130 PCT/EP2007/050678 -2 And because parts are formed with heat and rotation, rather than pressure, molds don't need to be engineered to withstand the high pressure of injection molding. Production costs for product conversions are reduced because lightweight plastics replace 5 heavier, often more costly materials, which makes rotational molding as cost effective for one-of-a-kind prototypes as it is for large production runs Rotational molding is versatile and able to handle a vast variety of shapes and sizes. Many parts cannot be readily produced by any other method. Typical examples are specialty tanks 10 and containers for fuel, water, and chemical processing, livestock feeders, drainage systems, food service containers, instrument housings, vending machines, highway barriers and road markers. Other application areas are consumer products, toys and transportation. Many aspects of the rotational molding process are, for example, described by R. J. Crawford and J. L. Throne in Rotational Molding Technology, Plastics Design Library, William Andrew 15 Publishing, 2001. As mentioned above rotational speed, heating and cooling times may be all controlled throughout the process. The maximum temperature of the air, which is reached inside the hollow molded article, depends strongly on the heating time. This temperature is also called 20 peak internal air temperature (PIAT). It correlates with the temperature of the molten resin. The concept of peak internal air temperature (PIAT) and the consequences, if a too low or too high PIAT is applied, is for example described by M. C. Cramez et al. in Proc. Instn Mech. Engrs. Vol. 217 Part B: J. of Engineering Manufacture, 2003. 25 The peak internal air temperature can influence the final properties of the molded product. For example, if the temperature becomes too high, a strong yellowing may occur and also the mechanical properties are negatively affected, for example, the impact strength decreases significantly. If the temperature remains too low the final properties can also be 30 adversely affected because the resins have not been properly molten. In other words, there is only a small temperature range for achieving the desired final properties. It is therefore of high interest to widen this temperature range or processing window, within which almost constant mechanical properties are obtained.

WO 2007/088130 PCT/EP2007/050678 -3 Botkin et al in "An additive approach to cycle time reduction in rotational molding" Rotational Molding by Design Conference, Society of Plastics Engineers, 2004 have demonstrated that by using a proprietary process stabilizer, the PIAT can be shifted towards lower temperatures maintaining good impact strength. This corresponds to broadening the processing window 5 towards lower temperatures. Surprisingly it has now been found that when a secondary hindered amine compound is added to the resin formulation a significantly broader processing window towards higher temperatures is achieved without adversely affecting color and mechanical properties of the 10 molded article. Consequently one aspect of the invention is the use of a secondary sterically hindered amine compound as processing additive for enlarging the processing window towards higher peak internal air temperatures in rotational molding processes of thermoplastic polymers. 15 Under processing window there is understood the temperature range, as measured by the peak internal air method (PIAT), within which the mechanical properties and/or the color of the molded article remain essentially the same. A particularly suitable mechanical property to measure is impact strength, for example at low temperatures. Low temperature means in 20 this context from 00 to -500 C, particularly -200 C to -400 C. For example the sterically hindered amine is a compound containing at least one group of the formula (1) or (II)

CH

3

G

1 CH 3

G

1

G-CH

2 G2

G-CH

2 G2 25 HN HN N-*

G-CH

2 G - CH 2

CH

3 CH 3 in which * indicates a bond G is hydrogen or methyl, and 30 G 1 and G 2 , independently of one another, are hydrogen, methyl or together are a substituent =0.

WO 2007/088130 PCT/EP2007/050678 -4 For instance the sterically hindered amine is a compound containing at least one group of formula (la).

CH

3

CH

3 HN

CH

3

CH

3 (la). 5 The sterically hindered amine compounds are known and widely used as thermal or light stabilizers for polymers. They are either commercially available or can be prepared as described, for example, in US-A-5,679,733, US-A-3,640,928, US-A-4,198,334, US-A-5,204,473, US-A-4,619,958, US-A-4,110,306, US-A-4,110,334, US-A-4,689,416, 10 US-A-4,408,051, SU-A-768,175 (Derwent 88-138,751/20), US-A-5,049,604, US-A-4,769,457, US-A-4,356,307, US-A-4,619,956, US-A-5,182,390, GB-A-2,269,819, US-A-4,292,240, US-A-5,026,849, US-A-5,071,981, US-A-4,547,538, US-A-4,976,889, US-A-4,086,204, US-A-6,046,304, US-A-4,331,586, US-A-4,108,829, US-A-5,051,458, WO-A-94/12,544 (Derwent 15 94-177,274/22), DD-A-262,439 (Derwent 89-122,983/17), US-A-4,857,595, US-A-4,529,760, US-A-4,477,615, CAS 136,504-96-6, US-A-4,233,412, US-A-4,340,534, WO-A-98/51,690 and EP-A-1,803, the disclosures of which are incorporated by reference. 20 Preferred are the following commercial compounds. Chimassorb 2020@, Chimassorb 944@, Tinuvin 770@ and Tinuvin 783®, Cyasorb UV 3346®, Cyasorb UV 3581@, Dastib 845®, Dastib 1082@, Diacetam 5, Fero 806-X@, Goodrite 3034@, Goodrite 3150@, HALS IC-TAM, Hostavin N 20@, Hostavin N 24®, Hostavin N 30@, HOls S 25 95@, ICI PA 500@, Lichtschutzstoff UV 31, Luchem HA-B 18®, Mark LA 55@, Mark LA 57@, Mark LA 67®, Mark LA 68®, Sanduvor 3050@, Sumilizer 61@, Sumilizer 70@, Suimisorb TM 61@, UVASORB HA 88®, Uvinul 4049@, Uvinul 5050@, Uvasil 299®, Uvasil 125@. These compounds are commercially available and described in: US-A-5,679,733, US-A 30 3,640,928, US-A-5,204,473, US-A-4,619,958, US-A-4,110,306, US-A-4,110,334, US-A 4,689,416, US-A-4,408,051, SU-A-768,175 (Derwent 88-138,751/20), US-A-5,049,604, US- WO 2007/088130 PCT/EP2007/050678 -5 A-4,769,457, US-A-4,356,307, US-A-4,619,956, US-A-5,182,390, GB-A-2,269,819, US-A 4,292,240, US-A-5,026,849, US-A-5,071,981, US-A-4,547,538, US-A-4,976,889, US-A 4,086,204, US-A-6,046,304, US-A-4,331,586, US-A-4,108,829, US-A-5,051,458, WO-A 94/12,544 (Derwent 94-177,274/22), DD-A-262,439 (Derwent 89-122,983/17), US-A 5 4,857,595, US-A-4,529,760, US-A-4,477,615 (CAS 136,504-96-6), US-A-4,340,534, WO-A 98/51,690, EP-A-1,803, the disclosures of which are incorporated by reference, The sterically hindered amine compound according to the invention is preferably added in an amount from 0.01 to 5%, more preferably from 0.05 to 2% and most preferably from 0.1 to 10 1 % by weight, based on the weight of the thermoplastic polymer. For instance the thermoplastic polymer is a polyolefin, a polyvinylchloride or a polyamide. Examples are given below. 15 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, po lybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh 20 molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE). Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, prefe rably polyethylene and polypropylene, can be prepared by different, and especially by the 25 following, methods: a) radical polymerisation (normally under high pressure and at elevated temperature). b) catalytic polymerisation using a catalyst that normally contains one or more than one 30 metal of groups IVb, Vb, Vib or Vill of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either c- or a-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(Ill) chloride, alumina or silicon oxide. These WO 2007/088130 PCT/EP2007/050678 -6 catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, Ila and/or Illa of the Periodic 5 Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC). 10 2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE). 3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, 15 for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copo lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g. 20 ethylene/norbornene like COC), ethylene/1-olefins copolymers, where the 1-olefin is gene rated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vi nylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as 25 hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethy lene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyal kylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example 30 polyamides. 4. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides WO 2007/088130 PCT/EP2007/050678 -7 starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an ela stomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides 5 with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems). 10 Particular preference is given to polyethylene preferably linear low density polyethylene (LLDPE). For example the peak internal air temperature range in rotational molding processes is enlarged up to 10 to 500 C, preferably up to 15 to 40' C towards higher temperatures. The 15 reference being without the addition of a sterically hindered amine. Preferably the peak internal air temperature range is from 210 to 250' C, more preferably from 215 to 250' C and most preferably from 220 to 250' C. 20 The above temperature range corresponds to the preferred processing window, within which the mechanical properties and/or the color of the article are not adversely affected. In a specific embodiment of the invention an additional stabilizer selected from the group consisting of a UV-absorber, a sterically hindered amine, different from that of formula (1) or 25 (II), a phenolic antioxidant, a phosphite or phosphonite and a benzofuranone or indolinone is present. Examples for the above mentioned additives are given below. 30 1. Antioxidants 1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-di methyl- WO 2007/088130 PCT/EP2007/050678 -8 phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1' methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures there 5 of. 1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4 nonylphenol. 10 1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxy phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-bu tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hy 15 droxyphenyl) adipate. 1.4. Tocopherols, for example a-tocopherol, p-tocopherol, y-tocopherol, 6-tocopherol and mixtures thereof (vitamin E). 20 1.5. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2 methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide. 25 1.6. Alkylidenebisphenols, for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2' methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(a-methylcyclohexyl) phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4 methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butyl phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(a-methylben 30 zyl)-4-nonylphenol], 2,2'-methylenebis[6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'-methy lenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4 methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4 hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert- WO 2007/088130 PCT/EP2007/050678 -9 butyl-4'-hyd roxyphenyl)butyrate], bis(3-tert-butyl-4-hyd roxy-5-methyl-phenyl)d icyclopenta diene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephtha late, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphe nyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 5 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane. 1.7. 0-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydi benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy 3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4 10 tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxy benzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate. 1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy d roxybenzyl)malonate, d i-octadecyl-2-(3-tert-butyl-4-hyd roxy-5-methylbenzyl)malonate, di 15 dodecylmercaptoethyl-2,2-bis (3,5-d i-tert-butyl-4-hyd roxybenzyl)malonate, bis[4-(1,1,3,3-te tramethylbutyl)phenyl]-2,2-bis(3,5-d i-tert-butyl-4-hyd roxybenzyl)malonate. 1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame 20 thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol. 1.10. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy anilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tri azine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris 25 (3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyben zyl)isocyanu rate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-d imethylbenzyl)isocyan urate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy phenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)iso cyanurate. 30 1.11. BenzVlphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy droxybenzylphosphonate, d ioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

WO 2007/088130 PCT/EP2007/050678 -10 1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N (3,5-d i-tert-butyl-4-hyd roxyphenyl)carbamate. 5 1.13. Esters of p-(3,5-di-tert-butyl-4-hydroxvphenvl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9 nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hy droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol 10 propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.14. Esters of p-(5-tert-butyl-4-hVdroxV-3-methVlphenVl)propionic acid with mono- or poly hydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanedi ol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, 15 diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyl olpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; 3,9-bis[2-{3-(3-tert butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5] undecane. 20 1.15. Esters of p-(3,5-dicVclohexVl-4-hVdroxyphenVl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, tri ethylene glycol, pentaerythritol, tris(hyd roxyethyl)isocyanu rate, N,N'-bis(hydroxyethyl)ox 25 amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy droxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alco hols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, 30 ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyan urate, N,N'-bis(hydroxyethyl)ox amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy droxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane.

WO 2007/088130 PCT/EP2007/050678 - 11 1.17. Amides of p-(3,5-di-tert-butyl-4-hydroxyphenvl)propionic acid e.g. N,N'-bis(3,5-di-tert butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxy phenylpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hy drazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Nau 5 gard"XL-1, supplied by Uniroyal). 1.18. Ascorbic acid (vitamin C) 1.19. Aminic antioxidants, for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-bu 10 tyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3 methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicy clohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phe nyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N' 15 phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenyl amine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naph thylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-butyl aminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4 20 octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylamino methylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetra methyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenyl amino)propane, (o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenyl 25 amines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyl diphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro 3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert butyl/tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octyl-phenothiazines, 30 N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene. 2. UV absorbers and liqht stabilizers WO 2007/088130 PCT/EP2007/050678 -12 2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example 2-(2'-hydroxy-5'-methylphenyl)-benzo triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe nyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphe 5 nyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2' hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis-(a,a-di methyl benzyl)-2'-hyd roxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy 5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyl oxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2 10 methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-meth oxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonyl ethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxy phenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl 2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis[4-(1,1,3,3 15 tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3'-tert-bu tyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; [R-CH 2 CHj-COO-CH 2

CH

2 , where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotri azol-2-ylphenyl, 2-[2'-hydroxy-3'-(a,a-di methyl benzyl)-5'-(1, 1, 3,3-tetramethylbutyl)-phenyl] benzotriazole; 2-[2'-hydroxy-3'-(1, 1, 3,3-tetramethylbutyl)-5'-(a,a-d methyl benzyl)-phenyl]ben 20 zotriazole. 2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives. 25 2.3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxyben zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate. 30 2.4. Acrylates, for example ethyl a-cyano-pp-diphenylacrylate, isooctyl a-cyano-p,p-diphe nylacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-p-methyl-p-methoxycinna mate, butyl a-cyano-p-methyl-p-methoxy-cin namate, methyl a-carbomethoxy-p-methoxycin- WO 2007/088130 PCT/EP2007/050678 -13 namate, N-(p-carbomethoxy-p-cyanovinyl)-2-methylindoline, neopentyl tetra(a-cyano-P, p-di phenylacrylate. 2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis[4-(1,1,3,3-tetramethyl 5 butyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphe nylundecylketoxime, nickel complexes of 1 -phenyl-4-lauroyl-5-hydroxypyrazole, with or with 10 out additional ligands. 2.6. Sterically hindered amines, for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1 -octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperi 15 dyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl) 2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-di chloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetra methyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetrame 20 thylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethyl piperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1 ,3,8-triazaspiro[4.5]decane-2,4-dione, bis(1-octyl oxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1 -octyloxy-2,2,6,6-tetramethylpiperidyl)succi nate, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene 25 diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino) ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) 1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetrame thyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyr 30 rolidine-2,5-dione, 3-dodecyl-1 -(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6 dichloro-1,3,5-triazine, a condensate of 1,2-bis(3-aminopropylamino)ethane and 2,4,6 trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.

WO 2007/088130 PCT/EP2007/050678 -14 [136504-96-6]); a condensate of 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268 64-7]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethyl-4 piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro 5 [4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxo spiro-[4,5]decane and epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbo nyl)-2-(4-methoxyphenyl)ethene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, a diester of 4-methoxymethylenemalonic acid with 1,2,2,6,6 pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperi 10 dyl)]siloxane, a reaction product of maleic acid anhydride-a-olefin copolymer with 2,2,6,6 tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine, 2,4-bis[N-(1 cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino 1,3,5-triazine, 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperi dine, 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvor (Clariant; CAS 15 Reg. No. 106917-31-1], 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, the reaction product of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidine-4-yl)butylamino]-6-chloro-s triazine with N,N'-bis(3-aminopropyl)ethylenediamine), 1,3,5-tris(N-cyclohexyl-N-(2,2,6,6 tetramethylpiperazine-3-one-4-yl)amino)-s-triazine, 1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6 pentamethylpiperazine-3-one-4-yl)amino)-s-triazine. 20 2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy 5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted 25 oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides. 2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl) 1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2 (2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyl 30 oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4 methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl) 1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2 [2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2 hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4- WO 2007/088130 PCT/EP2007/050678 -15 (dodecyloxy/tridecyloxy-2-hyd roxypropoxy)-2-hyd roxyphenyl]-4,6-bis(2,4-d imethylphenyl) 1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl phenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydr oxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2 5 hydroxypropoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl 1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4 dimethylphenyl)-1,3,5-triazine, 2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4-methoxy phenyl)-1,3,5-triazine. 10 3. Metal deactivators, for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine, N, N'-bis(3,5-di-tert-butyl-4-hyd roxyphenyl propionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide. 15 4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phos phite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di 20 cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythrito diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythrito diphosphite, tristea ryl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 6 isooctyloxy-2,4,8,1 0-tetra-tert-butyl-1 2H-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert 25 butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethy phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, 2,2',2"-nitrilo [triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-te tra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy) 1,3,2-dioxaphosphirane. 30 The following phosphites are especially preferred: Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos"168, Ciba Specialty Chemicals Inc.), tris(no nylphenyl) phosphite, WO 2007/088130 PCT/EP2007/050678 -16 (0H 3

)

3 0 O(0H 3

)

3

(CH

3

)

3 C C(CHA) o 0 (A H 3 -OH P-F P-0-CH CH- N(B (CA C (OH 3 ) LC 33 C~ C(CHA ) 3 (0HA) 3 O(0H 3

)

3 0 P-O OH OH(0 4

H

9 )0H CH 3 (C) (0H 3

)

3 0 C O(0H 3

)

3 (0H 3

)

3 // o+o\ /-- "" (0H 3 ) O(0H 3 )C (C0H/ 3 3) 3 (D O(0HA) (0H 3

)

3 0 HOC /P )C \P-

OH

3 (E) -OL \0 0/ o-3

C(CH

3

)

3 (0H 3

)

3 0 WO 2007/088130 PCT/EP2007/050678 -17

CH

3

H

3 C - C - CH 3 o O (F) H37C/ O-P P-0-C 8H37 0 -P-OCH2CH3 (G) o O O H3C C. 0CH 3

H

3 C "CH

OH

3 - 2 5. Hydroxylamines, for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N dioctyihydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N 5 dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydrox ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine. 6. Nitrones, for example, N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl 10 alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnnitrone, N hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-al pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxyl amine derived from hydrogenated tallow amine. 15 7. Thiosynerqists, for example dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate or distearyl disulfide. 8. Peroxide scavengers, for example esters of p-thiodipropionic acid, for example the lauryl, 20 stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(p dodecylmercapto)propionate. 9. Polyamide stabilizers, for example copper salts in combination with iodides and/or phos 25 phorus compounds and salts of divalent manganese. 10. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali WO 2007/088130 PCT/EP2007/050678 -18 metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate. 5 11. Nucleatinq agents, for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). Especially 10 preferred are 1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1,3:2,4-di(paramethyl dibenzylidene)sorbitol, and 1,3:2,4-di(benzylidene)sorbitol. 12. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, car 15 bon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers. 13. Other additives, for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents. 20 14. Benzofuranones and indolinones, for example those disclosed in U.S. 4,325,863; U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839, EP-A-0591102; EP-A-1291384 or 3-[4-(2 acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxy 25 ethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)ben zofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-di methylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di tert-butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3 dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2-acetyl-5-isooctylphenyl)-5-isooctyl 30 benzofuran-2-one. The above additives are in general applied in an amount between 0.01 and 2% by weight based on the weight of the thermoplastic polymer.

WO 2007/088130 PCT/EP2007/050678 -19 A further aspect of the invention is a method for enlarging the optimal peak temperature range in rotational molding processes of thermoplastic polymers by the use of a secondary sterically hindered amine compound as processing additive. 5 Accordingly disclosed is a method for enlarging the processing window towards higher peak internal air temperatures in rotational molding processes of thermoplastic polymers, which method comprises incorporating a secondary sterically hindered amine into a thermoplastic polymer and subjecting the polymer to a rotational molding process.. 10 Yet another embodiment of the invention is a process for the production of thermoplastic hollow articles, which process comprises mixing a thermoplastic polymer with a secondary sterically hindered amine and subjecting this mixture to a rotational molding process where the peak internal temperature range is from about 215 to about 250C, 15 wherein when the thermoplastic polymer is polyethylene, the hindered amine is not a linear or cyclic condensate of N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine. Definitions and preferences given above apply also for the other aspect of the invention. 20 The following examples illustrate the invention. Example 1: Preparation of Polyolefin Hollow Articles by a rotational molding process 100 parts medium density polyethylene, copolymerized with hexene (nominal melt index 3.3 25 g/10 min., density 0.938 g/cm 3 ) are dry blended with 0.050 parts of zinc stearate and a combination of additional stabilizers as given in Table 1. The mixtures are melt compounded into pellets at 190 0C in a Superior/MPM extruder using a 24:1 L/D screw with Maddock mixing head at 100 rpm. The compounded pellets are ground to a uniform particle size (150 500 ptm) prior to the rotational molding process. This grinding step increases the surface area 30 of the particles leading to faster heat absorption, and thus reducing overall energy consumption. The rotational molding process is performed in laboratory scale equipment FSP M20 "Clamshell". The ground resin is placed in an aluminum mold, which is rotated biaxially in a gas fired oven. Hot air is circulated by blowers in the chamber while the temperature is increased to 2740C. This temperature is maintained for a specific time, which WO 2007/088130 PCT/EP2007/050678 -20 will give a certain peak internal air temperature (PIAT) as given in Table 2. Subsequently, the oven is opened and while still rotating, the mold is cooled with forced air circulation for 7.3 minutes, followed by water spray mist for 1.5 minutes, air cooling for 2 minutes, water spray 2.9 minutes and air cooling 4.4 minutes. Throughout the entire heating and cooling cycles, 5 the speed of the major axis is maintained at 6 rpm with a 4 : 1 ratio of rotation. After the cooling cycles, the mold is opened and the hollow object removed. The processing range is defined as peak internal air temperature range (PIAT) in which a part with high impact strength can be produced. The impact strength is measured with the Dynatup Falling weight method (251b/20"") according to ASTM D-3763 at -40' C. 10 Table 1 Additives 01 02 03 04 comparative 05 comparative 06 Zn-stearate 0.05 0.05 0.05 0.05 0.05 0.05 @lrgastab FS042 0.05 0.05 0.05 0.05 0.05 0.05 @lrgafos 168 0.12 0.12 0.12 0.12 0.12 0.12 @Tinuvin 622 0.12 @Cyasorb UV 3346 0.2 @Chimassorb 944 0.2 0.15 @Chimassorb 2020 0.2 @Chimassorb 119 0.08 @Hostavin N 30 0.2 @Tinuvin 770 0.05 Table 2: Results 01 02 03 04 comp. 05 comp. 06 Upperend of 227 229 229 216 219 238 processing window PIAT [0C] Total Impact Energy at -40 0C 44 45 47 46 50 43 Sterically hindered amine Sec. Sec. Sec. Tertiary Tertiary Sec. The data clearly indicate that the useful process range can be significantly shifted towards 15 higher temperatures by the use of secondary sterically hindered amine compounds without sacrificing the impact strength. Example 2: Preparation of Polyolefin Hollow Articles by a rotational molding process The procedure given in example 1 has been repeated with further additives as outlined in 20 Table 3. The results are presented in Table 4 WO 2007/088130 PCT/EP2007/050678 -21 Table 3 Additives 00 07 08 Zn-stearate 0.05 0.05 0.05 @IRGANOX 3114 0.05 0.05 0.05 @IRGAFOS 168 0.1 0.1 0.1 @TINUVIN 622 None 0.2 None @TINUVIN 783 None None 0.2 Table 4 00 07 08 Upperend of 198 210 221 processing window PIAT [*C] Total Impact Energy 45 42 42 at -40 *C [J] HALS NONE tertiary secondary /tertiary 5 Whereas the processing temperature, as measured by the peak internal air temperature, (PIAT) should not exceed 1980 C if no sterically hindered amine is present, 2100 are acceptable when a tertiary sterically hindered amine is present. However, this temperature can further be extended up to 2210 C, when, according to the invention, a secondary sterically hindered amine has been added. 10 @Irganox 3114 is a phenolic antioxidant from Ciba Specialty Chemicals, @Irgastab FS042 is N,N-di(tallow alkyl)hydroxylamine from Ciba Specialty Chemicals, @Irgafos 168 is a trisaryl phosphite from Ciba Specialty Chemicals, @Tinuvin 622 is a tertiary sterically hindered amine from Ciba Specialty Chemicals, 15 @Cyasorb UV 3346 is a secondary sterically hindered amine from Cytech Industries, @Chimassorb 944 is a secondary sterically hindered amine from Ciba Specialty Chemicals, @Chimassorb 2020 is a secondary sterically hindered amine from Ciba Specialty Chemicals, @Chimassorb 119 is a tertiary sterically hindered amine from Ciba Specialty Chemicals, @Hostavin N 30 is a tertiary sterically hindered amine from Clariant, 20 @Tinuvin 770 is a secondary sterically hindered amine from Ciba Specialty Chemicals, @Tinuvin 783 is a mixture of a secondary and tertiary sterically hindered amine from Ciba Specialty Chemicals.

Claims (11)

1. Use of a secondary sterically hindered amine compound as processing additive for enlarging the processing window towards higher peak internal air temperatures in rotational 5 molding processes of thermoplastic polymers.

2. Use according to claim 1 wherein the sterically hindered amine is a compound containing at least one group of the formula (1) or (II) CH 3 G 1 CH 3 G 1 G-CH 2 G2 G-CH 2 G2 10 HN HN N-* G-CH 2 G - CH 2 CH 3 CH 3 in which * indicates a bond G is hydrogen or methyl, and 15 G 1 and G 2 , independently of one another, are hydrogen, methyl or together are a substituent =0.

3. Use according to claim 2 wherein the sterically hindered amine is a compound containing at least one group of formula (la). CH 3 CH 3 20 HN CH 3 CH 3 (la).

4. Use according to claim 1 wherein the sterically hindered amine compound is added in an amount from 0.01 to 5% by weight, based on the weight of the thermoplastic polymer. 25

5. Use according to claim 1 wherein the thermoplastic polymer is a polyolefin, polyvinylchloride or polyamide. WO 2007/088130 PCT/EP2007/050678 - 23

6. Use according to claim 1 wherein the thermoplastic polymer is polyethylene.

7. Use according to claim 1 wherein the peak internal air temperature range in rotational molding processes is enlarged up to 10 to 500 C towards higher temperatures. 5

8. Use according to claim 1 wherein the peak internal air temperature range is from 215 to 2500 C

9. Use according to claim 1 wherein in the rotational molding process an additional stabilizer 10 selected from the group consisting of a UV-absorber, a sterically hindered amine, different from that of formula (1) or (II), a phenolic antioxidant, a phosphite or phosphonite and a benzofuranone or indolinone is present.

10. A method for enlarging the processing window towards higher peak internal air 15 temperatures in rotational molding processes of thermoplastic polymers, which method comprises incorporating a secondary sterically hindered amine into a thermoplastic polymer and subjecting the polymer to a rotational molding process.

11. A method of using a secondary sterically hindered amine compound as processing 20 additive for enlarging the processing window towards higher peak internal air temperatures in rotational molding processes of thermoplastic polymers.